Mechanism of the enhanced degradation of pentachlorophenol by ultrasound in the presence of elemental iron

Ultrasound combined with elemental iron (US/Fe(0)) is effective in oxidizing organic contaminants in water. The sonolysis degradation of pentachlorophenol (PCP) was significantly enhanced by a factor of 4.2 with the addition of elemental iron, mainly via reaction with hydroxyl radicals (OH radicals), and the synergistic mechanism of the enhancement in the combined system was investigated. Experiments were performed with (1) sole ultrasonic treatment; (2) ultrasound in presence of iron; (3) ultrasound combined with copper powder as the same particle size as iron powder; (4) ultrasound in presence of Fe(II). It was observed that PCP degradation and OH radicals production were both enhanced in these combined methods, and the pitting on the sonicated iron surface was apparent. These results indicated that the rate enhancements in US/Fe(0) system were attributed to (1) the iron solid effect and the catalysis of Fe(II) produced from corroded-iron with promoting the production of OH radicals; (2) the increased surface area of iron particles by acoustic cavitation with promoting the adsorption process.     

Decolorization of methyl orange by ozonation in combination with ultrasonic irradiation

The combination of ultrasound and ozone for the decolorization of azo dye, methyl orange, was studied. The effect of ultrasonic power, ozone gas flow rate, gaseous ozone concentration, initial dye concentration, pH and hydroxyl radical scavenger on the decolorization of methyl orange was investigated. The results showed that the synergistic effect was achieved by combining ozone with ultrasonic irradiation for the decolorization of methyl orange. The synergistic effect was more significant when the system temperature was raised due to the heat effect of ultrasonic irradiation. The decolorization of methyl orange fits the pseudo first order kinetic model. The decolorization rate increased with the increase of ultrasonic power, ozone gas flow rate, gaseous ozone concentration. However, the decolorization rate decreased with the increasing initial dye concentration. Either pH or sodium carbonate has little effect on the decolorization rate, indicating that the low frequency ultrasound enhanced ozonation process for the decolorization of methyl orange is mainly a direct reaction rather than radical reaction.     

Dioxygen in combination with hydrazine: a practical system for degradation of a broad spectrum of toxic organics in water

Green and cost-effective eradication of pollutants from water is an important and long-standing goal in environmental chemistry. A broad spectrum of toxic organics in water was efficiently destroyed in the presence of dioxygen in combination with hydrazine hydrate at 150 °C. Under this operating condition, two typical classes of toxic organic chemicals, phenols and nitrobenzene derivatives were totally destroyed. The mineralization rate of these organics was 35-86%. Furthermore, when this degradation system was applied to degradation of actual waste water of wood pulp bleaching with chlorine (COD: 1830 mg/L), 77% COD decrease and 52% TOC mineralization of the wastewater were observed. In each case, the major degradation products are small molecular compounds, such as methanol, formic acid and acetic acid except CO/CO₂. In the case of chlorophenols degradation, no dioxins and any other toxic compounds are detected by ¹H NMR. After degradation reaction, the hydrazine was also decomposed into N₂ and H₂O, and no remaining hydrazine is found.     

Study of the degradation behaviour of dimethoate under microwave irradiation

In this work, the degradation of dimethoate under microwave irradiation assisted advanced oxidation processes (MW/oxidants) were studied. The efficiencies of the degradation of dimethoate in dilute aqueous solutions for a variety of oxidants with or without MW irradiation were compared. The results showed that the synergistic effects between MW and K(2)S(2)O(8) had high degradation efficiency for dimethoate. Simultaneously, UV/TiO(2)/K(2)S(2)O(8) photocatalytic oxidation degradation of dimethoate was investigated. The experimental results indicated that the method of microwave degradation of organic pollutants in the presence of oxidant could reduce reaction time and improve product yield. Microwave irradiation was an advisable choice for treating organic wastewaters and has a widely application perspective for non- or low-transparent and fuscous dye wastewaters.     

水合肼还原法制备钴纳米棒

以表面活性剂聚乙烯吡咯烷酮（PVP）为软模板，采用水合肼作还原剂还原钴盐制备出钴纳米棒，通过XRD、XPS、TEM等分析手段对其结构和形貌进行了表征。结果表明：这种方法制备出来的钴纳米棒长度约为3-4μm，直径约为70～100nm，具有hcp晶相和fcc晶相，其含量比例约为1：1。     

Vertically aligned Fe-doped ZnO nanorod arrays by ultrasonic irradiation and their photoluminescence properties

A facile sonochemical route was demonstrated for the direct fabrication of Fe-doped ZnO nanorod arrays on a Si substrate under ambient conditions. By adding Fe³⁺ ions in reaction solution, Fe is readily in situ doped into ZnO nanorod arrays via ultrasound irradiation. The morphology and structural characteristic of the Fe-doped ZnO nanorods were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). And crystal structure was characterized by X-ray diffraction (XRD) spectroscopy. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) confirmed the Fe-doping of ZnO nanorod arrays with a concentration of 0.9 wt.%. In addition, Fe-doped ZnO nanorod showed the enhancement of photoluminescence (PL) intensity in green-yellow emission.     

Catalytic peroxygen activation by biosynthesized iron nanoparticles for enhanced degradation of Congo red dye

In this study, biogenic iron (Fe) NPs (B-Fe) were synthesized using Terminalia Bellirica plant extracts and used to activate persulfate (PS) and peroxymonosulfate (PMS) oxidants for degradation of Congo red (CR) dye. Chemogenic Fe-NPs (C-Fe) were also synthesized using borohydride reduction method for comparison. The synthesized Fe NPs were characterized for their surface morphology using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS)-based particle size analysis. Biogenic B-Fe NPs were more uniform in size and smaller (67–125 nm), compared to chemogenic C-Fe (59–277 nm), due to the capping effect of the biomolecules in plant extracts. Degradation efficiencies using the nanoparticle – oxidant system followed the order: C-Fe-PMS (86%) ∼ B-Fe-PMS (83%) > C-Fe-PS (75%) > B-Fe-PS (63%). Post-degradation UV–Vis absorbance spectra indicated the absence of intermediates in the PS/PMS systems, suggesting complete mineralization of the dye. The kinetics of the process is best described by shifting order rate kinetics. Alkaline pH conditions, low oxidant loading and high initial dye concentration hindered degradation kinetics, while catalyst loading had minimal impact on the oxidation process. The data strongly suggested that biogenic Fe NPs activated oxidant system is an effective alternative to existing hydroxyl – radical based advanced oxidation processes.     

水合肼还原氧化石墨烯的研究

通过改进的Hummers法制备氧化石墨,将获得的氧化石墨进行热剥离以及超声剥离得到双层甚至单层的氧化石墨烯片.然后采用化学还原-水合肼还原的方法去除氧化石墨烯所含的羧基COOH、羟基OH、羰基C=O和环氧基等化学基团.本实验着重研究了还原剂的用量和反应时间对各个化学基团的影响规律.     

Enhanced photocatalytic degradation of organic contaminants over CaFe_2O_4 under visible LED light irradiation mediated by peroxymonosulfate

A simple sol-gel approach is proposed herein to fabricate CaFe₂O₄for the degradation of various organic pollutants(rhodamine B(RhB),tetracycline hydrochloride,humic acid,and methylene orange)under LED light irradiation mediated by peroxymonosulfate(PMS).The results indicate that the calcination temperature can significantly influence the performance of CaFe₂O₄for PMS activation,and the CaFe₂O₄sample obtained at 800℃(CaFe₂O₄-800)exhibits the best efficiency in degrading RhB,which is much higher than that of Fe_2o₃-800.This can be attributed to the efficient separation of photogenerated electrons(e^-)and holes(h⁺)by PMS,which is validated by transient photocurrent response and photoluminescence measurements.Results from density functio nal theo ry calculations indicate that the valence band of CaFe₂O₄-800 exhibits a high concentration of carriers and weak localization of electrons,which are favorable for PMS activation.Radical scavenging results confirm that h⁺and O₂^·-are the dominant reactive species.Moreover,CaFe₂O₄-800 not only demonstrated a stable performance during eight cycling runs with negligible iron leaching but also exhibited excellent degradation efficiency under natural water and sunlight.Finally,the mechanism and pathway of RhB degradation by the CaFe₂O₄-800/PMS/LED system are also proposed.This work presents the enormous prospect of CaFe₂O₄as an environmentally benign photocatalyst for PMS activation.     

Formation of molecular nitrogen and diazene by electron irradiation of solid ammonia

We present an experimental study on 500-3000 eV energy electron irradiation of ammonia ice at 20 K. While molecular nitrogen and diazene (N₂H₂) were detected during post-irradiation thermal desorption no appreciable traces of hydrazine (N₂H₄) were observed. We suggest that the recombination between adjacent nitrogen atoms and between neighboring NH radicals can be the main mechanism responsible for the formation of the observed molecules, whereas hydrazine formed by two amino radicals is probably in an excited state and decays into diazene and hydrogen.     

Catalysis of advanced oxidation reactions by ultrasound: a case study with phenol

The present study is about the enhancement in ozone-mediated degradation and UV (254nm) photolysis of phenol in aqueous solutions by 300kHz acustic cavitation and the selection of operating parameters for optimum phenol removal efficiency. The method was based on monitoring of the concentration of phenol during 90min exposure to ozonation, sonication, UV photolysis, O(3)/ultrasound, UV/ultrasound and O(3)/UV/ultrasound operations. It was found that ozonation at alkaline pH was an effective method of phenol destruction, but it was considerably more effective when applied simultaneously with ultrasonic irradiation. The observed synergy particularly at alkaline pH was attributed to combined effects of: (i) increased ozone mass transfer (upon hydrodynamic shear forces created by ultrasonic bubbles) and (ii) excess hydroxyl radical formation (upon thermal decomposition of ozone in the gaseous cavity bubbles). Degradation of phenol by photolysis alone was negligible, while combination of UV-irradiation and ultrasound rendered considerable degrees of decay. The synergy here was explained by excess hydroxyl radicals that are formed by photolysis of ultrasound-generated H(2)O(2). Maximum rate of phenol degradation was observed in case of combined application of ozone, UV and ultrasound at basic pH.     

Kinetics and mechanism of degradation of p-chloronitrobenzene in water by ozonation

The kinetics and mechanism of p-chloronitrobenzene (pCNB) degradation by ozone were investigated. With reference compounds, nitrobenzene (NB) and chlorobenzene (CB), reaction rate constants of pCNB with O3 and OH were measured by means of competition kinetics (mixtures of pCNB and NB, or pCNB and CB), with the rate constants being, 1.6 L mol(-1) s(-1), 2.6 x 10(9) L mol(-1) s(-1), respectively. During the ozonation process of pCNB, an increase of chloride and nitrate ions in the water sample solution was observed, which is consistent with the decrease in pCNB concentration. But the total organic carbon (TOC) removal rate is not consistent with the pCNB elimination rate indicating only part of pCNB was mineralized and thus presumably some intermediate products were formed. The pCNB degradation intermediate products were analyzed by gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), high performance liquid chromatography (HPLC) and ion chromatography (IC). The main intermediate products were phenol, p-chlorophenol, p-nitrophenol, 2-chloro-5-nitrophenol, 5-chloro-2-nitrophenol, 5-nitro-catechol, para-benzoquinone, 5-nitro-1,2,3-trihydroxy phenol, trihydroxy semiquinone, glycolic acid, oxalic acid, hydroxybutanoic acid, mesoxalic acid, tartrouic acid, malonic acid, maleic acid, hydroxymalonic acid, tartaric acid, malic acid, ketoglutaric acid and muconic acid. From the identified reaction products, a possible degradation pathway for the ozonation of pCNB has been proposed.     

Optimal degradation processes control by two-level policies

Two-level control policies are applied to various types of Markov processes describing degrading parameters of system units. To estimate the system operation cost an expectation of losses per unit time is evaluated. It is assumed that the degradation process is observable, and a monitoring system can signal about future failures. Firstly, semi-Markov processes are considered. A death process is proposed for a unit subjected to corrosion. A Markov chain are used for the problem of fatigue crack growth. The control problem is studied mainly in a steady-state regime for units of multiple use when the cost function is performed as the ratio of expectations. The cost function as the expectation of losses per unit time for single units is also studied, and the majorizing property of this cost function is shown.     

A kinetic model for the degradation of benzothiazole by Fe3+-photo-assisted Fenton process in a completely mixed batch reactor

The degradation of benzothiazole in aqueous solution by a photo-assisted Fenton reaction has been studied in a batch reactor in the pH range 2.0–3.2 and for H₂O₂ and Fe(III) concentrations respectively between 1.0×10⁻³–1.5×10⁻¹ and 1.0×10⁻⁶–4.0×10⁻⁶ M.

A kinetic model has been developed to predict the decay of benzothiazole at varying reaction conditions. The use of kinetic constants from the literature in the model allows to simulate the system behavior by taking into account the influence of pH, hydrogen peroxide, Fe(III) and sulfate concentrations and the ionic strength.     

超声辐射丙烯酸丁酯无皂乳液聚合

利用超声辐射特殊的空化、乳化效应,实现了在不加引发剂的情况下丙烯酸丁酯的无皂乳液聚合,借助TEM、FT-IR、粒度仪观察其微观结构、粒度大小和分布,研究了超声功率对聚合物转化率的影响,分析了其形成的机理,表明了超声辐射是一种比常规乳液聚合更有效的物理技术.     

Rapid degradation of biomedical magnesium induced by zinc ion implantation

The degradation rate is important to biodegradable magnesium materials. In this study, Zn is implanted using a cathodic arc source into pure magnesium at an accelerating voltage of 35 kV. The nominal ion implant fluence is 2.5 × 10¹⁷ ions cm⁻². After Zn implantation, the degradation rate in simulated body fluids is increased significantly. It is postulated that because Zn exists in the metallic state in the implanted layer, the galvanic effect between the Zn rich surface region and magnesium matrix induces the observed accelerated degradation.     

Decoloration of aqueous Brilliant Green by using glow discharge electrolysis

This paper described a plasma degradation of Brilliant Green (BG) by glow discharge electrolysis. Various influencing factors such as the voltage, the distance between cathode and anode were examined. Ultraviolet (UV) absorption spectra, gas chromatogram-mass spectrum (GC-MS), and chemical oxygen demand (COD) were used to monitor the degradation process and to identify the major oxidation intermediates. It was confirmed that benzoic acid, 1,2,3,4,5,6-cyclohexanehexaol, and carboxylic acids (e.g., oxalic acid, succinic acid and hydroxyacetic acid) were produced in the degradation process. The results showed that BG rapidly underwent degradation and eventually mineralized into CO(2) and H(2)O.     

Formation of hydrogen peroxide by galena and its influence on flotation

The formation of hydrogen peroxide (H₂O₂), an oxidising agent stronger than oxygen, during the grinding of galena (PbS) was examined. It was observed that galena generated H₂O₂ in the pulp liquid during wet grinding and also when the freshly ground solids were placed in water immediately after dry grinding. The generation of H₂O₂ during either wet or dry grinding was thought to be due to a reaction between galena and water, when the mineral surface is catalytically active, to produce OH free radicals by breaking down the water molecule. It was also shown that galena could generate H₂O₂ in the presence or absence of dissolved oxygen in water.The concentration of H₂O₂ formed increased with decreasing pH. The effects of using mixtures of pyrite or chalcopyrite with galena were also investigated. In pyrite–galena mixture, the formation of H₂O₂ increased with an increase in the proportion of pyrite. This was also the case with an increase in the fraction of chalcopyrite in chalcopyrite–galena mixtures. The oxidation or dissolution of one specific mineral rather than the other in a mixture can be explained better by considering the extent of H₂O₂ formation rather than galvanic interactions. It appears that H₂O₂ plays a greater role in the oxidation of sulphides or in aiding the extensively reported galvanic interactions. This study highlights the necessity of further study of electrochemical and/or galvanic interaction mechanisms between pyrite and galena or chalcopyrite and galena in terms of their flotation behaviour.     

Coupling extraction–flotation with surfactant and electrochemical degradation for the treatment of PAH contaminated hazardous wastes

The performance of a two-stage process combining extraction of polycyclic aromatic hydrocarbons (PAHs) with an amphoteric surfactant (CAS) followed by electro-oxidation of PAH-foam concentrate was studied for the decontamination of aluminum industry wastes (AIW) and polluted soils. The PAH suspensions extracted from AIW and soils were treated in a 2 L-parallelepipedic electrolytic cell containing Ti/RuO₂ anodes and stainless steel cathodes. Current densities varying from 4.6 to 18.5 mA cm⁻² have been tested with and without addition of a supporting electrolyte (6.25 to 50 kg Na₂SO₄ t⁻¹ of dry waste). The best performance for PAH degradation was obtained while the electrolytic cell was operated during 90 min at a current density of 9.2 mA cm⁻², with a total solids concentration of 2.0%, and in presence 12.5 kg Na₂SO₄ t⁻¹. The application of the process on AIW (initial PAH content: 3424 mg kg⁻¹) allowed extracting 42% of PAH, whereas 50% of PAH was electrochemically degraded in the resulting foam suspensions. By comparison, 44% to 60% of PAH was extracted from polluted soils (initial PAH content: 1758 to 4160 mg kg⁻¹) and 21% to 55% of PAH was oxidized in the foam suspensions. The electrochemical treatment cost (including only electrolyte and energy consumption) recorded in the best experimental conditions varied from 99 to 188 USD $ t⁻¹ of soils or AIW treated.